Incorporation of couplers in nongelatin emulsions



J. A. LEERMAKERS ETAL Filed 001:. 26, 1940 INCORPORATION OF COUPLERS IN NON-GELATIN EMULSIONS GELATl/l-COUPLER COMPOUND. \CELLULOSE EJTER EMUL5 -suPPo/eT.

5 LUE SENS/T/VE CELLULOSE ESTER EMULS/ON. YELLOW F/LTER.

GEL A-T/N- C OUPL E R COMPOUND.

6EL/4T//Y- COUPLER COMPOUND GREEN SENS/T/I/E CELLULOSE ESTER EMULSION. GELAT/N-COUPLER COMPOUND.

sup/ eer.

RED SENS/ T/VE CELL ULOSE ESTER EMULSION JQHNA. LEERMAKERS \5cHEw2/Ne 5.

lEAKE INVENTORS BY mafia /1 TTORNE YS opaque or translucent material such as paper) described in that application, an acid halide of carries a plurality, preferably three, of difiera coupler was reacted with a protein such as entially color-sensitized emulsions, one or more gelatin under conditions which produced a comor all of which contain color couplers, i. e., bodies pound of the protein and the coupler capable of which are capable of combining with the oxidaielline- This method involve th use f such tion product of the developing agent used for reaction conditions, for example, time and temdeveloping the exposed silver salt to metallic silperature f r a n, t at t p n s t ver with the production of coloring matter in the r app e b degraded and ed W t region where the silver is developed. Subsequent pier t pr du a mp und f th up r and removal of metallic silver without removal of the p te n which wo d je d which Co d be coloring matter leaves substantially clear transmixed with gelatin emulsions to form an emulsion parent dye images. capable of rendering a colored image upon suit- It is known that in materials of this kind able developmentare cast in layers such as one upon another, or particular in emulsions of silver halide in certain where they are dispersed in the form of differce u ose e The eomilollmlsi When S0 disentially color-sensitized grains in a single body persed, have still less tendency to wander from of a binder such as gelatin. Attempts have been the emulsion in which they a e orporated than made to avoid this difiiculty by introducing a in the case of gelatin emulsions. The physical group into the molecules of the couplers designed dissimilarity between gelatin and cellulose esters to .render them non-difiusing, either by increasis a distinct advantageas regardsthe wandering ofing'the molecular weight or by giving them some compounds of the former from layer to layer in degree of substantivity to the gelatin. multi-layer coatings of the layer. The chemical It is therefore, an object of the present indifficulties between the gelatin and the cellulose vention, to provide a method for incorporating ester is also an improvement over dispersions of couplers in silver halide emulsions. A further a gelatin compound in gelatin. 1 object is to provide a method for incorporating The dispersing medium suitable for use with couplers in non-gelatin emulsions. A still furour invention includes cellulose nitrate and In!- FFECE UNi'l STATES PATENT INCORiORATION 0F COUPLERS IN NONGELATHN EMULSIUNS John A. Leermakers and scheming S. Fierke, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application Gctober 2b, 1M0, Serial No. 353,012 in Great Britain December 29, 1939 7 Claims. (Cl. 95-7) This invention relates to color couplers and sectional view of a multi-layer photographic eleto color photographic elements containing them. ment made according to our invention.

In particular the invention relates to color pho- In Russell and Staufier U. S. Patent 2,282,001, tographic elements of the type in which a supgranted May 5, 1942, a method for the preparaport (which may be of transparent material such 5 tion of color forming compounds non-diffusing in as cellulose nitrate or cellulose acetate or of gelatin was described. According to the method cliificulty. arises from the fact that the couplers 20 It h s now been found that color formers tend to wander from the emulsions with which which have been combined W t t n o ot they are incorporated into the adjacent emulsion protein s described in Russe and Staufier Patwhereby the true color rendered is detrimentally ent 2,282,001, can be dispersed in emulsions of affected. This is the case where the emulsions silver halide in vehicles other than gelatin and in ther object is to provide a method for incordrolyzed cellulose organic acid esters of approxiporating couplers in non-gelatin emulsions so mately 19% to approximately 33% acyl content.

that they will not difiuse in multi-layer coat- Hydrolyzed esters having an acyl content of from ings. Other objects will appear from the fol- 19% t 2 are particularly s f l due to their lowin d script n of our inventionhigh water permeability.- A method for prepar- These objects are accomplished by mixing with ing dispersions of silver halide in esters of this a non-gelatin emulsion such as an emulsion of type is described in Salo U. S. Patent 2,110,491, silver halide in a hydrolyzed cellulose organicacid March 3 1939 ester of approximately to approximately The following examples, which are illustrative 3 acy Content, a compound o gelatin and a only, indicate methods of forming emulsions accoupler capable of reacting with the development cording t our inventinn; product of aprimary aromatic amino coupl n Emmple 1 developing agent.

In the accompanying drawing, Fig. 1 is a sec- A coupler-gelatin compound made as described tional view of asingle layer photographic element in Russell and Stauffer U. S. Patent 2,282,001,

made according to our invention and Fig. 2 is a comprising 10 grams of l-acetoxy-naphthalenethe vehicle.

-su1fjonyl gelatin was placed in 300 cc. of cold distilled water for four hours. The water was then drained off and the gelatin coupler was melted on a steam bath to produce 160 cc. of solution. When a portion of this solution was treated with a portion of the following developer and a small amount of potassium periodate, a deep blue-green color was produced showing that the coupler was capable of forming a colored image upon treatment. with the oxidation product of a coupling developer.

2-amino 5 diethylamino toluene hydrochloride grams 2.0 Sodium sulfite do 2.0 Sodium carbonate do 20.0 Potassium bromide do 2.0 Water cubic centimeters 1000.0

80 cc. of the gelatin-coupler solution, containing 5 grams of the gelatin-coupler compound, were aded to 95 cc. of a silver bromide emulsion in which cellulose acetate propionate having an acyl content of about 20% was used as This emulsion contained approximately 2% grams of silver bromide. A plate was coated with the emulsion coating the dispersed gelatin coupler and, after drying and exposure, were developed in the developing solution described above. A blue-green image was produced.

Example 2 An emulsion made as described in Example 1 was sensitized with 5-4-(3-ethyl-2(3)-benzothiazolylidene) -2-butenylidene-3 n heptyl 1 phenyl-2-thiohydantoin to produce red sensitivity. This emulsion was coated on a plate and dried. An emulsion was then placed in a similar manner by using as the coupler 2-cyano acetyl-naphthalene-x-sulfonyl gelatin, a magenta coupler. This emulsion was sensitized to green light with 5- (3-ethyl-2- (3) -benzolylidene) ethylidenel-S-n-heptyl 1 phenyI-Z-thiohydantoin. This emulsion was coated over the red sensitized emulsion and dried. This plate was then exposed under a step tablet to red light and to green light and to both green and red light together. The plate was then developed in the developer described in Example 1. Those areas exposed to red light produced a blue-green dye only, those areas exposed to green light yielded a magenta dye only and where mixtures of red light. and green light were used for exposure, a combination of blue-green and magenta dyes was produced. Similarly a blue-sensitive emulsion, which need not be optically sensitized, and which would contain a yellow gelatin-coupler compound, could be coated over the emulsions described above to produce a complete multicolor element.

The preparation of the sensitizing dyes referred to in Example 2 is described in Brooker U. S. Patent 2,282,116, granted May 5, 1942.

Our invention will now be described by reference to the accompanying drawing. As shown in Fig. 1, ID is a support of transparent material such as cellulose acetate or cellulose nitrate or opaque material such as paper, having thereon an emulsion layer ll of silver halide dispersed in a water permeable cellulose ester and containing particles l2 of a gelatin coupler compound. Fig. 2 shows a multi-layer element in which the support is coated with emulsion layers l3, l4 and I5 of silver halide dispersed in a water permeable cellulose ester and sensitive, respectively. to the red, green and blue regions of the spectrum. The element will contain the usual yellow filter layer l6 between layers l4 and I5. Layer l3 of this element. contains particles ll of gelatin and blue-green coupler, layer I4 contains particles I8 of gelatin and magenta coupler and layer 15 contains particles l9'oi gelatin and yellow coupler. This element may be developed to a colored image directly after exposure or may be developed first in a black and white developer, then developed in a color forming developer to produce colored images in the remaining silver halide of the element.

In addition to the formation of sensitive emulsions by incorporation of couplers in dispersions of silver halide in cellulose esters, filter and antihalation layers may also be formed according to our invention by incorporating reaction products of dyes and gelatin in cellulose esters.

The examples referred to herein are understood to be for purposes of illustration only and our invention is to be taken limited only by the scope of the appended claims.

We claim:

1. The method of preparing a color-forming photographic emulsion which .comprises mixing with an emulsion of silver halide in a hydrolyzed cellulose organic acid ester of approximately 19% to approximately 33% acyl content; a compound of gelatin and a coupler capable of gelling and also capable of reacting with the development product of a primary aromatic amino coupling developing agent.

2. The method of preparing a color-forming photographic emulsion which comprises mixing with an emulsion of silver halide in a hydrolyzed cellulose acetate of approximately 19% to approximately 33% acetyl content, a compound of gelatin and a coupler capable of elling and also capable of reacting with the development product of a primary aromatic amino coupling developing agent.

3. The method of preparing a color-forming photographic emulsion which comprises mixing with an emulsion of silver halide in a hydrolyzed cellulose acetate propionate of approximately 19% to approximately 33% acyl content, a compound of gelatin and a coupler capable of gelling and also capable of reacting with the development product of a primary aromatic amino coupling developing agent. g

4. The method of preparing a color-forming photographic emulsion which comprises mixing with an emulsion of silver halide in a hydrolyzed cellulose organic acid ester of approximately 19% to approximately 33% acyl content, a naphthalene sulfonyl gelatin coupler capable of gelling and also capable of reacting with the development product of a primary aromatic amino coupling developing agent.

5. A photographic emulsion capable of producing a colored image upon development in a primary aromatic amino coupling developing agent. which comprises a hydrolyzed cellulose organic acid ester of approximately 19% to approximately 33% acyl content containing a sensitive silver halide and a compound of gelatin and a coupler capable of gelling and also capable of reacting with said developing agent.

6. A photographic emulsion capable of pro ducing a colored image upon development in a primary aromatic amino coupling developing agent, which comprises a hydrolyzed cellulose acetate of approximately 19% to approximately 33% acetyl content containing a sensitive silver halide and a. compound of gelatin and a coupler capable of gelling and also capable of reacting v with said developing agent.

7. A photographic emulsion capable of producing a. colored image upon development in a primary aromatic amino coupling developing agent,-

which comprises a hydrolyzed cellulose acetate 5 reacting with said developing agent.

JOHN A. LEERMAKERS. SCHEURING S. FIERKE. 

